Water in oil emulsions containing 1, 2-alkanediols as coupling agents



latented Aug. 122, i952 I:

Wm TAT PATENT. I HC WATER 'IN' on." EMULs-IoNs CONTAINING I IQZ-ALKANEDIOLS' AS COUPLING AGENTS 1 Philip James Garner, Wirral', and Philip'Alan Q vWinsor, Great vSutton, England, assignors to V j Shell ;Development Company, San Francisco,

I g I Calif.,acorporation of Delaware I g f No -Drawing. Application June-8, 1 94's, S erialNo.

1 31,828.; I1'1GreatBritainJune23,1947 I I s'ciai i s. Cl. 252-305} 1 y A a =Theipresent invention relates to improvements agent in, or affinity for, aqueous or oleaginous inemulsificationand emulsifying compositions. media. Such adjusting function has led to the The invention relates more particularly to. ,comdescription of 'such substances as coupling. positionscomprising oil, an emulsifying agent, agents. It has now been found that 1 ,2-alkaneand; a couplin agent imparting substantially. 5 diols, that is, the saturated aliphatic dihydric alimproved" characteristics to the composition. cohols the hydroxy groups'of which are attached The suitability of emulsions and emulsifying to :the, ultimate and adjacent penultimatev car compositions for use on apractical scale is govbon atoms of the carbon chain, and having at erned tono small degree by properties and char- 7 least seven carbon atomstothe molecule; possess acteristics imparted to them by individual com- 10 to an outstanding degree the ability to adjust the ponents therein. Thu oil emulsions, such .as, solubility of the emulsifier in, or the relative af-v for example, oil in water or water in oil emulfinity of the emulsifier fonaqueous or oleaginous sions,cprepared with the aid of emulsifying agents media, t are often lacking in a sufficient degree of sta- 7 It has been found that emulsions comprising bility. This is often particularly so where the oil, water, and an emulsifying agent of substan emulsifying composition-or emulsion is prepared tially improved stability are obtained by the with: theiaid of. synthetic organic emulsifying incorporation therein of .a 1, 2-alkanediol having agents. Inthe case of an emulsion consisting. at least seven carbonatoms. The presence of essentially of oil, water, and a specific concentrathe:,l,2-alkanediols having at least seven carbon tion of a given emulsifier; two important factors atoms, it has been found, enables the obtaining influencing stability'are therespective amounts of emulsions comprising oil and water of unof the two phases and the solubility of the emule usual stability even with the aid of such emulsis-ifier in the oil and water. at the prevailing temfiers as the synthetic organic emulsifying agents perature conditions. When, as is often the. case, having a greater solubility in, or affinity for, such an emulsion serves as the base for other. inwater than for the oil to be emulsified.

gredients-having. some essential industrial func- Without intent to limit the scope of the inven} tion, such as :an insecticidal, fungicidal, phartion by any theory advanced'herein to set forth maceutical, veterinary or a corrosion inhibitingv more fully the nature of the invention, it is befunction, the factors governing stability of the lieved that the coupling agents-used in thecomcomposition become more complex. Suchaddipositions of the present invention, by reason of tional components which may be'dissolved or dis their carbon chain and physical and chemical persed in the oil or water phase, often influence p pe S p to exhibit a higher So ubi ty the solubility of the emulsifying agent in that in, or affinity for, oil than for water and to modiphase; and by reason of their. essential chemical V the Solub li y or afinity characteristics of the or physical characteristics these additional inemul ify agent without in anyw y inhibitinggredients will often exhibit va tendency to renthe emulsifyin properties of the emulsifier. The der unstablean otherwise stable emulsion. The fi i cy 0f nalkanediol, it has beenfoundrdeproduction of such emulsions with the aid of creases as t e hydro yl oups recede from the commercially. available synthetic organic. emulend of the carbon chain, and molecules in which sifying agents, which will possess stability char- 40 the two hydroxyl groups are located in the 1,2- acteristics of a degree enabling practical use, positions exhibit decidedly superior effectiveness often presents considerable difiiculties. as coupling agents than do any other isomeric Underlying many of these difiiculties is the configura The high i i ncy of the 1,2-

circumstance that the relative solubility of the alkanediols Of seven 01 more carbon atoms is beemulsifying agent in, or the relative affinity of lievedattributable to the free orientation of the the emulsifier for, water'and oil differ to-a degree diol molecules at the surface of he o l parwhich militates against any permanence of the cles. H wev t outstanding behavior o dispersion. Many of the commercially available the class of c pl agents emp oyed in the comynthetic r a i emulsifying agents suffer in positions of. the present invention could in no this respect and exhibit g, greater solubilitydn, .50 Wise be predicted from that which was hitherto or ,afiinity f or, aqueous media than they do for known in respect f h Products.

oleaginous media. 7 An. effective coupling agent needs to possess -It .is any object of the present invention to various other p operties apart from those alrea y provide meanswhereby these adverse charactermentioned if it is to be capable of wide, useful istics of such emulsifyin agents can be modified. industrial application. For instance, it should in a manner which enables their being used efhave a relatively low melting point in order to fectively and with greater certainty to provide facilitate handling and mixing and in order that t b 11 l i it ma not tend to crystallize out from the emul- Substances are known which have the-ability sifying compositions or finished emulsions on of adjusting the solubility of the emulsifying cooling. In this respect the 1,2-a1kanediols at ordinary conditions of temperature and pres- A coupling agent should preferably be.

sure. odorless; this is particularly so in many industrial applications of the emulsions containing it, for

example, in pharmaceutical preparations, and in.

soluble cutting oils. 1,2-alkanediols of the present invention exhibit substantial advantage over many of the substances which have been proposed as .QQUplinsagents heretofore, such as the cresols, cyclohexanols and various monohydric alcohols which for the most part possess marked odor; Again, a satisfactory coupling agent should be capable of being: employed in a wide range of concentrations. Most coupling agents employed heretofore canon'lybe 'used effectively over a comparatively narrow range of concentrations outside of which range 'they tend to inhibit dispersibility. The 1,2-alkariediols employed in" the compositions of the present invention are substantially freefrom such limitation.

Illustrative of the -1,2 -alkanediols employed as coupling agents in the present-invention are the following compounds: 1,2-heptanediol, 1,2-octanediol, 2,5-dimethyl-1,2-hexanediol, 2-methyl- 1,2 octanediol, 1,2 decanediol, 2 methyl 1,2- nonanediol, 2 methyl- ,2-decanediol, 2-methyl- 1,2-undecan'ediol, 2 methyl-1,2-dodecanedibl, and their homolog-ues: Of the 1,2-alkanediols having at least seven' carbon atoms to the molecule those having from seven to fourteen carbon atoms are preferred. Preferred are the alcohols comprised within the above class illustrated by the formula wherein R. is analkyl group having from five to twelve carbon atoms. Particularly preferred are the alcohols comprised within the class illustrated by the above empirical formula wherein R'is a straight chain alkyl grouphaving from five to twelve carbon atoms. The latter particularly preferred compounds are illustrated by the 1,2-alkanediols corresponding to 1,2-heptene, 1,2- octene, l,2-nonene,-1,'2-decene, 1,2-undecene, 1,2- dodecene, l,2-tridece ne, and 1,2-'tetradecene. Of the suitable dihydric alcohols comprised within the group represented by the above empirical formula wherein R is of branched chain structure those wherein R contains an unbroken carbon chain of at least five carbons arepreferred.

-The emulsions and emulsifying compositions of the present inventionmay comprise a mixture of two or more of the 1,2-alkanediol coupling agents. The amount of the coupling agent employed may vary widely within the scope of the invention and will varyin accordance with the characteristics of the particular components, such as the oil, emulsifying agents and any other additives incorporated in the composition. Thus, the coupling agent may suitably be' added in amounts rangingpfor example, from about 1% to about 25% by volume of the oil component of the composition. Higher or lower proportions of the coupling agent may, however, be employed within the scope of the invention.

The 1,2-alkanediol coupling agents may be employed in combination with other coupling agents. Thus compounds such as, for example, monohydric alcohols, ethylene glycol, cresylic acids and the like may be added to the emulsions or In thisrespect also -theemulsifying compositions. Thus; the minimum temperature at which compositions comprising certain of the 1,2-alkanediols may be employed without fear of their crystallization may be or with a totallydifierent type of coupling agent.

This result may be obtained for example by combining a certain 1,2-alkanediol having a relatively high-melting point with a 1,2-alkanediol or other type of coupling agent having a substantially lower melting point. Thus 1,2-undecanediol, the

melting point of which is 48 C., may be mixed with 1, 2 -octanediol or with a mono-hydric alcohol such as lauryl alcohol to result in mixtures which remain liquid at 20 C. and lower and which are highly suited for use as coupling. agents ;in'.the

emulsions land emulsifying composition's I ;of .the'.

present invention .1:

The. 1,2-'alkanediols:employed in the datainvention may be obtained from. any suitable source. They may be conveniently prepared; for example; by the action of hydrogen-peroxide on the 1,2-olefin corresponding to the;,1,2'-a1kanediol desired, 'or mixtures of 1,2-olefins, in the;

presence of formicfacidji It: is toibe understood,v

however, that the invention is in'nowise limited to the utilization.o-f:1,2-alkanediols obtained by any specific method of preparation or from-any specific source.

A particular advantage of the invention resides in the'ability to producefemulsions ofimp'roved stability. with the aid of synthetic organic: emul-.

sifying agents. Examples :of such synthetic or-.

ganic emulsifying agents which may be incorporated in the emulsifying-compositions or emullsions comprised within the. scope of the .inven'-- tion include salts of sulfated aliphaticv alcoholscontaining at least seven carbon atoms. Included within the latter class. of emulsifying agentsare the salts of the secondary alkyl sulfuric acidsv obtained from olefins derived fromcra'cked paraffin wax, for example, by :theproces'ses described in U. S. Patents.2,078,516, 2,152,292, 2,139,393;

2,172,228. Further examples. of such synthetic organic emulsifying agents are thefsaltsiof primary alkyl sulfuric acids'prepared, for-example:

from naturally occurringyor. synthetic. fatty acid derivatives; thewatere'soluble salts oflalkyl aryl. sulfonic' acids, suchasjdodecyl benzene 'sulfonic.

acid;'.salts of hydrophilic. naphthasulfonates; salts ofalkyl or arylfphosphoric acids; salts'of carboxylic acids having :emulsifying properties;

cationic emulsifying. agents; non-ionic emulsifying agents such as polyethylene oxide derivatives; Theemulsifying agents are added in amounts sufiicientto obtain the desired de-- gree of emulsification; The amount added will of course vary in accordance 'withthe nature of the specific emulsifier employed as well as withthat of the individual components of the emultall oil; fatty acids; ammonium o'r alkali metal salts of naphthenic acids, of tall oils, or of fatty acids; etc.

\ The emulsifying compositions of this invention are employed in'the preparation of compositions of the soluble oil-, gel-, paste .solution-., or

droplet-emulsion'type for industrial, insecticidal,

fungicidal, pharmaceutical, veterinary and -do-' mestic purposes. In preparing the emulsifying compositions and emulsions comprised within the scope of the invention, the coupling agents may be added in part or entirety to the individual oil or emulsifier component, or to mixtures of the oil and emulsifier. In variations of the method of preparing the compositions the coupling agents may be dissolved in suitable solvents prior to addition to the oil and/or emulsifier components of the compositions. In the preparation of the emulsifying compositions concentrated compositions are usually first prepared to facilitate commercial distribution, although they are not generally employed in this form. Thus the emulsifying compositions of the present invention may be mixed with light mineral oils or lubricating oils to give soluble cutting oils of improved characteristics, particularly with respect to stability. Such soluble cutting oils are readily dispersed in practically all proportions of water to give extremely stable emulsions useful in the cold working of metals.

The term oil as employed in the present specification and appended claims to denote the oil component of the emulsifying compositions of the present invention is intended to include not only known mineral, vegetable and animal oils generally consisting wholly or substantially of carbon and hydrogen or of carbon, hydrogen and oxygen, but also oils modified by treatment such as the halogenated hydrocarbons, or organic liquids immiscible, or only slightly miscible, with aqueous media.

In the following examples, illustrative of, but not limiting the invention, all indicated parts are by volume unless otherwise stated.

Example I Five parts of spindle oil and 4.1 parts of emulsifier known by the trade name Teepol X consisting essentially of an aqueous solution containing about of sodium secondary alkyl (Cm-C13) sulfates and 6% sodium sulfate, are mixed with a solution of 1,2-undecanediol in lauryl alcohol to result in a cutting oil readily dispersible in water to form stable emulsions.

Example II diol resulting in a clear soluble cutting oil readily dispersible in water to form stable emulsions.

Example III a 6% sodium sulfate, are mixed with 0.6 part of 1,2-octanediol to result in an emulsifying composition which on the addition of 3 parts of carbon tetrachloride yields a stiff, clear gel readily dispersible in water.

Example IV Eight parts of carbon tetrachloride are mixed with two parts of emulsifier known by the trade name Teepol X and consisting essentially of an aqueous solution containing about 20% of sodium secondary alkyl (Cm-C13) sulfates and 6% of sodium sulfate, resulting in an unstable emulsion. 0.2 part of 1,2-octanediol are then added to the mixture and a clear stable dispersion results which can be further diluted with water without losing its stability.

The invention claimed is:

1. A Water in oil emulsion readily dispersible in water consisting essentially of a mineral oil, water, a water-soluble sulfate salt of an aliphatic alcohol containing from seven to about eighteen carbon atoms to the molecule, and 1,2- octanediol.

2. A water in oil emulsion readily dispersible in water consisting essentially of a mineral oil, water, a water-soluble secondary alkyl sulfate salt, and 1,2-alkanediol.

3. A water in oil emulsion readily dispersible in water consisting essentially of a mineral oil, water, a water-soluble secondary alkyl sulfate salt, and 1,2-octanediol.

4. A water in oil emulsion readily dispersible in water consisting essentially of a mineral oil, water, a water-soluble secondary alkyl sulfate salt, and a straight chain saturated aliphatic dihydric alcohol having the hydroxyl groups in the 1,2-positions and having from seven to fourteen carbon atoms to the molecule.

5. A water in oil emulsion dispersible in water consisting essentially of spindle oil, water, the sodium salt of a secondary alkyl sulfate, and 1,2- octanediol.

6. A water in oil emulsion dispersible in Water consisting essentially of spindle oil, water, a water-soluble sulfate salt of an aliphatic alcohol containing from seven to about eighteen carbon atoms in the molecule, and 1,2-octanediol.

7. A Water in oil emulsion dispersible in water consisting essentially of spindle oil, water, a water-soluble secondary alkyl sulfate salt, and 1,2-octanediol.

8. A water in oil emulsion dispersible in water consisting essentially of a mineral oil, water, a water-soluble sulfate salt of an aliphatic alcohol having from seven to about eighteen carbon atoms to the molecule, and a straight chain saturated aliphatic dihydric alcohol having the hydroxy groups in the 1,2-positions and having from seven to fourteen carbon atoms to the molecule.

PHILIP JAMES GARNER. PHILIP ALAN WINSOR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number 

1. A WATER IN OIL EMULSION READILY DISPERSIBLE IN WATER CONSISTING ESSENTIALLY OF A MINERAL OIL, WATER, A WATER-SOLUBLE SULFATE SALT OF AN ALIPHATIC ALCOHOL CONTAINING FROM SEVEN TO ABOUT EIGHTEEN CARBON ATOMS TO THE MOLECULE, AND 1,2-OCTANEDIOL. 